Abnormalities of the Halogen Bonds in the Complexes between Y2CTe (Y = H, F, CH3) and XF (X = F, Cl, Br, I)

• Published in: Molecules (Basel, Switzerland) Switzerland), 2022-12, Vol.27 (23), p.8523
• Main Authors: Wang, Ya-Qian, Wang, Rui-Jing, Li, Qing-Zhong, Yu, Zhi-Wu
• Format: Article
• Language: English
• Subjects: Abnormalities; abnormality; AIM; Chemistry; competition; halogen bond; hydrogen bond; Hydrogen bonding; Hydrogen bonds; Iodine; NBO; Polarizability
• ISSN: 1420-3049; 1420-3049
• DOI: 10.3390/molecules27238523

In this work, the hydrogen bonds and halogen bonds in the complexes between Y2CTe (Y = H, F, CH3) and XF (X = F, Cl, Br, I) have been studied by quantum chemical calculations. We found three interesting abnormalities regarding the interactions. Firstly, the strength of halogen bonds increases in the order of IF < BrF < ClF < F2. Secondly, the halogen bonds formed by F2 are very strong, with an interaction energy in the range between −199.8 and −233.1 kJ/mol. Thirdly, all the halogen bonds are stronger than the hydrogen bonds in the systems we examined. All these results are against the general understanding of halogen bonds. These apparent abnormal properties are reconciled with the high polarizability of the Te atom and the strong inducing effect of F on the Te atom of Y2CTe. These findings provide a new perspective on halogen bonds. Additionally, we also proposed bonding distance-based methods to compare the strength of halogen/hydrogen bonds formed between different donor atoms and the same acceptor atom.